Fabric conditioning

ABSTRACT

STALE FOAM FABRIC CONDITIONING AGENTS, PREFERABLY FABRIC SOFTENERS WHICH ALSO HAVE ANTISTATIC ACTIVITY, ARE MADE BY DISPENSING A PRESSURIZED COMPOSITION OF FABRIC CONDITIONING AGENT TO THE ATMOSPHERE, AFTER WHICH THE FOAN IS TUMBLED WITH FABRICS IN A AUTOMATIC LAUNDRY FERROUS PRODUCT, AS IT LEAVES THE ROLLING MILL AT A TEMPERATURE OF FROM BETWEEN 800*C TO 1200*C., IS SPRAYED WITHE MOST USEFUL SOFTENING COMPOSITIONS FOR THESE PRODDUCTS INCLUDE HIGHER FATTY ACYL AMIDOPROPYL DI-LOWER AKYL GLYCINES AND HIGHER FATTY ALKYL DI-LOWER ALKYL GLYCINES. PREFERABLY, THESE ARE FORMULATED WITH WATER AND A PLASTICIZER OR SOLVENT SUCH AS GLYCEROL, AND ARE PRESSURIZED WITH A MIXTURE OF LIQUEFIED GASES SUCH AS THOSE OF THE FREON OR LOWER HYDROCARBON TYPE.

US. Cl. 117139.5 CQ 6 Claims ABSTRACT OF THE DISCLOSURE Stable foamfabric conditioning agents, preferably fabric softeners which also haveantistatic activity, are made by dispensing a pressurized composition offabric conditioning agent to the atmosphere, after which the foam istumbled with fabrics in an automatic laundry dryer or similar machinewhile they are in a damp state, with hot drying air being circulatedthrough the dryer. The most useful softening compositions for theseprodducts include higher fatty acyl amidopropyl di-lower alkyl glycinesand higher fatty alkyl di-lower alkyl glycines. Preferably, these areformulated with water and a plasticizer or solvent such as glycerol, andare pressurized with a mixture of liquefied gases, such as those of theFreon or lower hydrocarbon type.

This invention relates to the conditioning of fabrics, such as thosewhich are made of cotton or synthetic fibers or mixtures thereof. Moreparticularly, it relates to such conditioning effected by stable foampreparations containing compounds which are effective as softeningand/or antistatic agents, with the foams being sufficiently stable towithstand several minutes of tumbling with the materials being treated,during which tumbling period conditioning agent is transferred to thematerials. The invention also is of the stable foams and the pressurizedcompositions from which they are produced, which preferably includederivatives of dimethyl glycine such as mixed higher fatty alkyl oracylamidoalkyl dimethyl glycines, and alkanolarnine higher fatty acidsoaps.

Fabrics, yarns, threads, manufactured textiles, articles, such asclothing, and laundry have all been treated at some stage of themanufacturing process or subsequently, to impart desirable properties tothem. Compositions for effecting such treatments have been produced invarious physical forms, including emulsions and sprays, and applicationshave been made at different temperatures and various conditions so as toproduce the best results. Among the treatments utilized have beenapplications of softening and antistatic agents to fabrics.

The treatment of laundry in the washing machine with chemicals forimproving the softness of the laundered fabrics is well known. Usually,substantive treating agents have been incorporated in detergentcompositions or have been dissolved in the wash water or rinse water.Among the most effective conditioning compounds used have been thecationic softening agents, often of the quaternary ammonium salt type,and in most effective commercial applications such softeners have beenadded to the laundry by being dissolved in the rinse water, aftercompletion of washing. Of course, this entails the disadvantage ofrequiring the user to be present at the end of the washing cycle andbefore the rinse water is discharged. In recent years, suchinconvenience has been avoided by having softening and antistatic agentsadded to the laundry after it has been transferred to an automaticdryer. Softening agents have been sprayed onto the laundry or onto dryerinterior parts, for subsequent transfer to the laundry. Fabricconditioning agents have been incorporated in cellulosic substrates.They have been applied from the surfaces of paper, cardboard, wood andplastic articles.

3,826,682 Patented July 30, 1974 have been discharged from aerosolcontainers and have been applied as foams to the laundry and tumbledwith it in an automatic laundry dryer, during which tumbling operationsthe conditioning agent is transferred to the laundry to be treated.Operations in the dryer are more advantageous than methods which requireaddition of softening agent in the rinse water. Thus, they allow the useof non-substantive softening and antistatic agents,.do not waste suchagents in discharged rinse water and are more convenient to employ.However, due to application to the laundry in somewhat concentratedform, in some cases the deposits of conditioning agent were not uniformand sometimes stains were apparent on the laundry, especially ifpressurized conditioners were discharged directly onto the materials tobe treated. To avoid, this, in a previous application for patent, Ser.No. 109,691, for Fabric Conditioning, by Roberts et al., filed in theUS. Patent Office on Jan. 25, 1971, a stable foaming conditioningcomposition was described in which the foam was formretaining, that is,it would maintain its shape for at least about five minutes (statictest) without being converted to liquid. In the dryer such foams wouldnot immediately deposit all their conditioning agent on the laundry butwould be abraded or worn down during the early part of the tumblingperiod. Such foams, containing fabric conditioners and foaming agents ofthe surface active types, were substantial improvements over liquids andother dispensable fluid products previously used in the dryer. However,although they were advances over the art at the time made, researchefforts have continued in an attempt to produce still better productswhich would satisfactorily condition laundry without unevenly applyingsoftener to it and without ultimately staining the laundry or buildingup hydrophobic deposits thereon which would give it a stiff or greasyfeel, as occurs with repeated applications of cationic conditioners fromfoams. As a result of this work, there have been discovered conditioningfoams of increased stability which can be applied to the laundry in anautomatic laundry dryer and will very satisfactorily condition itwithout causing any staining or objectionably uneven applications of theconditioning compounds and which do not make the treated materialshydrophobic or greasy after repeated applications.

In accordance with the present invention a fabric conditioningcomposition in a pressurized dispensing container comprises 1 to 20% ofa fabric conditioning compound of the formula wherein R is a higherfatty alkyl or mono-unsaturated alkenyl of 9 to 19 carbon atoms ifadjacent to and of one more carbon atom if adjacent to nitrogen, R ishydrogen or alkyl of 1 to 3 carbon atoms, R and R are alkyls of 1 to 3carbon atoms, m1 is from 1 to 5, n is 0 or 1 and p is from 1 to 3, 0.1to 30% of a fabric conditioning lower alkanolamine higher fatty acidsoap, 15 to of a liquefied gas or pressurized gas propellant for thecomposition, sufiicient to generate a pressure of from 10 to pounds persquare inch gauge, and up to 75% of water, which composition, ondispensing from a normally gasand liquid-tight container, produces along lasting stable foam useful for slowly and evenly distributing themixed fabric conditioning agents over the surfaces of fabrics with whichthe foam is brought into contact during a tumbling operation. Inpreferred embodiments of the invention the compound of the formula is acoconut oil fatty alkyls amine of dimethyl glycine or a coconut oilfatty acids amidopropyl dimethyl glycine, the soap is triethanolaminestearate, the propellant is a mixture of chlorofiuorinated hydrocarbonsand the compositions contain from 20 to 60% of water, sufficient to forman emulsion with the propellant but insufiicient to make the foamproduced by dispensing the pressurized composition, wet, soupy or fastbreaking. The invention also relates to the highly stable foams that aremade, which withstand the tumbling treatment of an automatic laundrydryer for over three minutes without completely disappearing, methodsfor making them and methods of conditioning fabrics with them.

Of all the fabric softening and antistatic agents known, those whichhave been found to produce the best stable foams and which mostsatisfactorily condition fabrics when applied as foams are derivativesof di-lower alkyl glycine, which may be in the betaine form, employed inconjunction with lower alkanolamine soaps. The glycine derivatives areof the formula wherein R is a higher fatty alkyl or mono-unsaturatedalkenyl, R is hydrogen or lower alkyl and R and R are lower alkyls. Thesubscripts m, n and p are numbers from 1 to 5, or 1, and 1 to 3,respectively. The higher alkyls R, or acyls all.

are of to carbon atoms, e.g., lauroyl, myristyl, palmitoyl, palmityl,stearoyl, stearyl, oleyoyl. R is usually hydrogen but may also be loweralkyl preferably of 1 to 3 carbon atoms, such as methyl, ethyl, n-propyland isopropyl, while R and R which may be same or different, are loweralkyls, also preferably of 1 to 3 carbon atoms, such as those describedfor R The most preferred alkyl for R and R is methyl. Although m may besuch as to produce an alkylene, e.g., methylene, ethylene, propylene,butylene or amylene, it has been found that the propylene embodiment,wherein m is 3, is preferred when n is 1. Whether it is 0 or 1, it isalso preferable that p be 1, although ethylene and propylene radicalsalso may usefully connect the nitrogen and the acyl carbon of thedimethyl glycine moiety.

The most preferred dialkyl glycine derivatives used are cocoylamidopropyl dimethyl glycine and cocoyl dimethyl glycine. The preferredfatty acid groups, which are mainly of 10 to 14 carbon atoms, but may beof 10 to 20 carbons, as the name indicates, are obtained from coconutoil fatty acids, as are the alkyls of the same carbon atom contents.Other synthetic and naturally occurring higher fatty acids that may beused, occur in tallow, corn oil, palm kernel oil, palm oil, greases, andvarious other vegetable oils and animal fats. These may be converted tothe corresponding fatty acids or alcohols or sometimes, may be used asthe triglycerides. They may be fractionated or purified to particularproducts, such as topped coconut oil acids, commercial stearic acid,double or triple pressed stearic acid, which then may be reacted toproduce the desired dialkyl glycine derivatives. In addition to thepreferred compounds, other materials which are also useful in thepractice of this invention, either alone or preferably, with thementioned preferred softening and antistatic agents, are coconut oilfatty acids amidomethyl dimethyl glycine; tallowyl amidopropyl dimethylbetaamino acid; stearoyl N-methyl amido-n-butyl di-n-propyl glycine,stearyl dimethyl glycine, cocoyl diethyl gammaamino acid and tallowyldimethyl betaamino acid.

The alkanolamine higher fatty acid soaps which are most useful incombination with the dialkylglycine derivative softening agents andwhich, together with them, produce softening and antistatic compositionsof greatly improved properties, are usually lower alkanolamine higherfatty acid soaps in which the lower alkanol is of 1 to 5 carbon atoms,preferably 1 to 3 carbon atoms and most preferably, is ethanol. Thehigher fatty acid portion of the molecule is of 10 to 20 carbon atomsand is preferably of 16 to 20 carbon atoms, with the 16 to 18 carbonatoms range being most preferred. The best embodiment of the fatty acidmoiety of the alkanolamine soap is commercial stearic acid, doublepressed, comprising stearic, palmitic and oleic acids, or triple pressedstearic acid, comprising stearic and palmitic acid. Of course, the purestearic or palmitic acids may be employed, if the cost thereof is notserious detriment. The alkanolamines of the alkanolamine soaps may bemono-, di-, or tri-alkanolamines and of these, the trialkanolamines aremost preferred. Generally, they are of the same alkanol radicals butmixed alkanolamines are also used. Instead of the alkanolamines, in somecases the lower alkyl amines may be employed, usually in mixture withthe alkanolamine soaps. Examples of the alkanolamine soaps are the mostpreferred triethanolamine stearate, triethanolamine palmitate,triethanolamine tallowate, triisopropanolamine cocate,tri-t-butanolamine laurate, diethanolamine stearate andmonoisopropanolamine palmitate.

Although the combination of the glycine derivative and the describedsoap gives the present compositions their highly improved properties, itis possible to mix in with them other conditioning agents, but generallythe proportion of such additional materials will be such that theycomprise a total of less than 30% of the final composition. Variousconditioning agents can be used but these will preferably be of thesurface active types, such as were described in US. patent applicationS.N. 109,851, previously mentioned. Usually, the cationic conditioners,al though considered in the prior art to be the best of the softeningagents, will be omitted because of some tendencies to stain or renderfabrics hydrophobic after repeated uses, due to continuing buildup ofthe substantive cationics. However, if desired, these may be employed,and if so, they will usually be quaternary ammonium compounds such asthose containing a plurality of lower alkyl groups on the quaternarynitrogen, together with one or two higher alkyls, benzyls or equivalentgroups thereon. The halogen will usually be chlorine or bromine. Amongthe quaternary compounds that may be used are distearyl dimethylammonium chloride, imidazolinium methosulfate compounds and stearylpyridinium halides. Amphoteric conditioners used include the complexfatty amido compounds, e.g., those sold as Soromines AT and AL, thehigher alkyl betaalanines, the N-higher alkyl aspartic acids and theMiranols.

Anionic surface active agents, including the sulfuric reaction productshaving a higher alkyl or acyl radical thereon, are also useful. Some ofthese compounds are the higher alkyl benzene sulfonates, preferably withthe alkyl being linear; the higher fatty acyl taurides and isethionates;higher fatty acid monoglyceride sulfates and sulfonates; and morespecifically, tallow alcohol sulfate, coconut oil monoglyceride sulfateand n-dodecyl benzene sulfonate, as the sodium salts. The preferredsurface active fabric softeners and antistatic agents are the nonioniccompounds, which include the polyoxy-lower alkylene higher alkyl ethers,e.g., polyoxyethylene lauryl ether having four ethoxy groups (Brij 30);higher alkyl phenoxy poly (lower alkoxy) lower alkanols, e.g., nonylphenoxy polyethoxy ethanol (Igepal CO 880) and balancedhydrophilic-lipophilic compounds made by the condensation of loweralkylene oxides with organic hydrophobic materials, e.g., Pluronics F-68and L-44. Such nonionic softeners usually include lipophilic groupshaving higher alkyl components, generally of 8 to 20 carbon atoms, andhydrophilic components which are poly-lower alkylene oxides of 4 tomoles of lower alkylene oxide per mole of compound. Preferred loweralkylene oxides are those of 2 to 3 carbon atoms, most preferably,ethylene oxide. The nonionics do not react with either the dimethylglycine derivatives or the soaps and therefore, are ordinarilypreferable supplementary conditioning agents for a variety of formulasof the present conditioning compositions.

In the recitations of anionic conditioning agents which can be used assupplemental softeners, the ordinary higher (C -C fatty acid soaps ofalkali metals, such as sodium and potassium, alkaline earth metals, suchas calcium, and the ammonium and magnesium soaps were not recited. Thesemay be used alone or in mixture, together with the alkanolamine soaps,but the proportions thereof will normally be held to less than 30% ofthe total higher fatty acid soap content.

With the dimethyl glycine derivative(s) and alkanolamine soap it hasbeen found that it is often desirable to incorporate a particular typeof nonionic softener. Thus, from 0.2 to 20% of the composition may be anamine oxide conditioning agent. The amine oxides are usually higheralkyl di-lower alkyl amine oxides wherein the higher alkyl is of 8 to 20carbon atoms, preferably of 12 to 18 carbon atoms, and the lower alkylis of 1 to 4 carbon atoms, preferably being methyl. Mixtures of alkylsmay also be employed. The amine oxides help to distribute the otherrequired conditioning agents satisfactorily over the materials beingtreated, contribute to non-staining properties and help to remove theconditioning agent on subsequent launderings, aiding in preventing thetreated textile or fabric from becoming hydrophobic or waterproofed.

Small proportions of higher fatty acid lower alkanolamides, especiallydi-lower alkanolamides also aid in conditioning and in producing andmaintaining a stable foam. Such compounds are of higher fatty acids of10 to carbon atoms, preferably of 12 to 18 carbon atoms and mostpreferably, of 12 to 14 carbon atoms, and of lower alkanols, such asthose of 1 to 4 carbon atoms, especially ethanol and isopropanol.Examples of suitable alkanolamides include lauric myristicdiethanolamide, the preferred compound; lauric diisopropanolamide;stearic monoethanolamide; myristic diethanolamide; palmiticmonoisopropanolamide and lauric dimethanolamide. Instead of the samealkanol being employed, different alkanols of the types mentioned may beused, as in lauric myristic ethanol isopropanolamide.

It has been found that the presence of a plasticizing, humectant oremollient type compound such as a suitable dihydric, trihydric orpolyhydric lower alkanol, e.g., glycols, glycerol, lower alkyleneglycol, dialkylene glycol, or polyalkylene glycol, such as propyleneglycol, diethylene glycol, dipropylene glycol, polyethylene glycol,sorbitol and mannitol, and equivalent such compounds and substitutedderivatives thereof, make satisfactory components of the presentcompositions and appear to toughen the stable foam produced, so as tomake it better able to resist the shocks and forces encountered intumbling with humid materials during the conditioning operation.

With the plasticizer or humectant it is sometimes also advisable toinclude in the present compositions other strengthening agents and alubricant. Materials which improve the strength of the foam includeresinous or polymeric compounds, such as gums and synthetic organicplastics, but these sometimes have the undesirable effect on the treatedfabrics of forming flakes or apparent deposits thereon, even whenemployed in small quantities. Similarly, the lubricants, as representedby mineral oils and waxes, produce deposits which, on subsequentironing, become oily or waxy stains. Yet, it has been found that aparticular polymer, when emulsified, is useful in leveling theconditioning agent over the materials treated and performs an importantlubricating function while still not diminishing appreciably thestrength of the foam or its life when tumbled in contact with theclothing to be treated. Although such emulsions may be made from otherpoly-lower alkylenes, such as polypropylene, it is highly preferred thatthe lubricant employed be a polyethylene emulsion in water. Such anemulsion usually comprises from 5 to 60% of the polyethylene, with thebalance except for a small amount of emulsifier being water. The usualemulsifiers, whether anionic, cationic, nonionic or amphoteric, may beemployed, providing that they do not react with or otherwise interferewith the other constituents of the foaming composition. However, thenonionics, e.g., polyethoxylated alkyl phenols, are preferred. Thepolyethylene will usually be of a molecular weight from 1,000 to 3,000and the percentage of emulsifier present will generally be from 0.2 to12%. Descriptions of various useful emulsifiers are found in thereference work Detergents and Emulsifiers 1969 Annual, by John W.McCutcheon.

The propellants used may be any suitable type, including compressedgases such as nitrogen, carbon dioxide, nitrous oxide and air butusually those that are most satisfactory for producing foams will beorganic compounds, generally lipophilic in nature and low boiling,usually being liquids near atmospheric pressures, which are referred toas liquefied gases. These will preferably be cyclic or acyclic lowerchlorocarbons, fluorocarbons, chloro-fiuoro carbons, or hydrocarbons ofcarbon contents of 1 to 4. Although such compounds may contains freehydrogens the best of them are saturated and completely halogenated.Examples of suitable propellants are those commercial products known asPropellants 11, 12, 14, 21, 22, 114, etc. Perhaps the most useful of theliquefied gas propellants are dichlorodifluoromethane,monofluorotrichloro methane, dichlorotetrafluoroethane,octafluoropropane octafiuoro cyclobutane, propane, butane, isobutanecyclobutane, methylene chloride, and tetrafluoromethane. The propellantswill usually be employed in mixture, with the mixture being such as togenerate a pressure in a gas-tight container of about 10 to 100 lbs./sq. in. gauge, preferably from 20 to 70 lbs/sq. in g. at 70 F. They willalso be chosen for compatibility with the rest of the formula and forassisting and maintaining the stability of the foams generated. Ifflammable propellants are used, considering that the nature of thepresent product is such as to require its employment in conjunction withlaundry dryers, they will usually be formulated with non-flammablematerials or other propellants so as to avoid any danger of combustionin use. In preferred propellant formulations there will be employed from10 to of a high pressure propellant and from 90 to 10% of a diluentpropellant. For example, 60 parts of dichlorodifiuoromethane may be usedwith 40 parts of dichlorotetrafluoroethane to make a propellant or gasportion of a conditioning composition. Preferably such ratios will befrom 70 to 30% of the high pressure propellant and 30 to 70% of the lowboiling diluent.

The water employed in the conditioning compositions, if present at all,will preferably be deionized or other water of low hardness, under 50parts per million of hardness, calculated as calcium carbonate. -It willusually be undesirable for it to contain dissolved salts to an extent ofmore than 0.1%.

Of course, with the other constituents there may be present variousadjuvants such as coloring agents (dyes and water dispersible pigments),perfumes, fluorescent dyes or optical brighteners, bactericides,fungicides, soil repellents, synthetic and natural gums and colloids,and solvents, all for their obvious functions. Usually, the total ofsuch materials will be less than 20% of the composition weight andpreferably, will be less than 5% thereof, \slv iyth no material beingpresent in an amount greater than To obtain a pressurized compositionthat will be dispensable to the atmosphere through an ordinary aerosolvalve to form a stable foam (one which will have at least 10% of itsweight still in foam form after three minutes of tumbling with a load ofclothing in an automatic laundry dryer) there will be employed from 15to 75% (composition basis) of a liquefied gas or pressurized gaspropellant, preferably 35 to 65%, and most preferably from 40 to 60%.The propellant will create a pressure in the range previously describedherein in referring to such materials and mixtures thereof. Thepropellant will be emulsified with the conditioning agent or will havethe agent dissolved in it. When water is present, to aid in theformation of an emulsion, there will be no more than 75% of it in thepressurized composition and preferably, the amount thereof will be from20 to 60%, with most preferable proportions being in the range of 30 to50%. The fabric conditioning compound of the formula given will comprisefrom 1 to 20% of the pressurized composition, preferably 1 to 15% andmost preferably about 2 to 5% thereof. Use of the concentrations of thepreferred range results in conditioning that is almost as good as whengreater quantities of the formula compounds are employed, a surprisingphenomenon. Thus, use of such low concentrations and amounts iseconomical, diminishes any possibility of staining or spotting of thetreated fabrics and minimizes any possible skin irritation or other harmfrom misuse of the product. The content of conditioner may be all of onecompound or can be a mixture of compounds within the given formula. Thetriethanolamine higher fatty acid soap will be from 1 to 30%, preferablyfrom 1 to of the composition. Other fabric softeners and antistaticagents which may be present will usually be limited to the proportionsmentioned previously, when they were discussed. Within the ranges givenit is preferred that the ratio of dimethyl glycine conditioningcompound(s) to alkanolamine soap should be in the range of 10:1 to 1:5preferably from 2:1 to 1:2.

The proportion of higher fatty acid alkanolamide will be from 0.05 to2%, preferably from 0.1 to 0.5% and that of humectant or plasticizerwill be from 0.1 to 20%, preferably from 1 to 10%. Too much alkanolamidemakes the product objectionably thick and interferes with uniformdispensing. Amine oxides may constitute from 0.5 to 20% of thecomposition, if present, and will preferably be from 1 to 5% thereof.Poly-lower alkylene emulsions, such as polyethylene emulsions may befrom 1 to if present, preferably from 2 to 10% thereof, on apolyethylene basis.

The proportions of constituents mentioned above are those which arefound to give useful softening and antistatic eifects while stillproducing the described stable foams which evenly distribute the activeconditioning agents over the surfaces of fabrics to be treated under theconditions encountered in the normal automatic laundry dryer. Also, suchcompositions do not stain the laundry, deposit greasy spots thereon(especially noticeable after ironing) or make the fabric hydrophobicafter repeated treatments, as the cationics of useful softening effectsmay do. When different materials are employed, outside the descriptionsgiven, or when proportions are changed so as to be outside the limitsrecited, properties of the compositions are altered and a lessacceptable product, generally unacceptably poorer in foaming andconditioning characteristics results. This is especially true if thequantities of conditioning agent are diminished or that of water isincreased so as to be outside the ranges given.

The stable foam made by discharging to the atmosphere the pressurizedcompositions of this invention very quickly (generally within 10seconds), resists breakdown or drainage, even in use in the automaticlaundry dryer. The constituent of the composition that is partiallyremoved in the generation of the foam is the propellant, which almostcompletely volatilizes, leaving a major fraction thereof forming thegaseous phase of the foam. Thus, the foam will be constituted of all theoriginal components except a small part of the propellant mixture,usually less than preferably less than 10% lost, and therefore, may besaid to comprise in parts what it originally comprised in percentages,except for a slight increase due to the propellant loss. On a percentagebasis, the proportion of each constituent will be increased bymultiplying the original percentage by 100-X, wherein X is the percentof propellant originally present.

The present aerosol compositions are readily prepared, requiring nospecial steps, apparatuses or methods. Soaps and surface active agentsalts may be made in situ or may be mixed with the rest of theingredients, except for the propellants, and the compositions maysubsequently be pressurized, usually by gaseous propellant being addedthrough a dispensing valve. Normally, initial mixing of materials is atroom temperature and they may be warmed sufficiently to produce ahomogeneous product. Also, in addition to pressure filling, cooledliquid propellant may be added to the container, after which thedispensing valve may be afiixed. In the making of the triethanolaminestearate in situ, triethanolamine and stearic acid may be blendedtogether initially or later in the formulation of the composition. Withrespect to heating to make the mixture homogeneous or to promote in situreactions of the types described, it will normally not be required toheat the mixture to a temperature higher than 50 C. Of course, withfugitive materials, such as perfumes and solvents, addition thereof willbe when most appropriate to avoid excessive evaporation losses. Althoughthe products may be made at any of various pHs, usually the pH of thesoftening composition, at 1% in water, will be from 6 to 10, preferablyfrom 7 to 9.

To use the pressurized composition one needs only to press the dischargevalve button of the aerosol dispenser to release the desired amount ofconditioning foam. For best results the can should be shaken immediatelyafter manufacture and also before use to make sure that the compositionis uniform before dispensing. This also will prevent undesired increasesin pressure due to separation of the propellant from the rest of theproduct. The foam may be discharged directly into the dryer onto fabricsor laundry to be conditioned, usually in a single mass or charge. Itneed not be first discharged externally of the dryer and thentransferred to the fabrics. Tumbling of the laundry and the dryingthereof may be commenced immediately after adding of the foam. Becausethe density of the foam will usualy be about constant for a particularcomposition, the consumer can judge by volume or dispensing time whenthe appropriate amount of foam has been generated.

The amount of conditioning composition employed will usually besufiicient to provide about 0.05 to 3 grams of the mentioned fabricconditioning compounds (within the formula, and alkanolamine soap) perpound of dry laundry and most preferably, about 0.1 to 1 gram per poundwill be used. Thus, for the usual eight lbs. of dry laundry in the dryerfrom 0.4 to 25 grams of conditioning agent will be used. Such relativelysmall amounts are convenient to handle, pack and dispense, and with theusual aerosol container several applications are available from a singlepackage. Even less of the glycine derivative conditioning agent isemployed, usually from 0.01 to 1 gram per pound dry laundry, preferably0.05 to 0.5 g./lb. Of course, the amounts to be used will depend on theelfectiveness of the particular conditioning composition. The amount ofconditioning agent present in the formula may be adjusted so as to allowfor a certain desired number of uses of the product per container.

The laundry treated will normally contain from 20 to 70%, most oftenfrom 30 to 60%, of water, with the balance usually being of mixedcotton, cotton-polyester, nylon, acetate, acrylic and Dacron textiles.Although such materials may be treated with the present foams outsidethe automatic laundry dryer, conditioning in the dryer appears to be farsuperior, apparently due to the tumbling effects, the wetness of thelaundry, the humid atmosphere, the air blowing and the presence of heat,and therefore is highly preferred.

Although the present stable foams will maintain their shapesindefinitely if not subjected to external forces, when added to the damplaundry in an automatic laundry dryer the foams are slowly abraded orworn down so that the conditioning materials in them are spread over thesurfaces of the laundry. Although other foams have been employed inwhich such spreading took place within one to five turns of the dryerdrum (about 0.5 to 15 seconds) or longer, the superior properties of thepresent compositions are thought to be due in significant part to a moreeven application of conditioner to the laundry and to a coaction betweenthe dialkyl glycine derivative conditioner and the alkanolamine soap, inthe foam form, which spreads the composition in thin smears over thelaundry and does not deposit greasy spots or strains. For example, in adrum which may revolve at a speed of from 10 to 100 rpm, most often from10 to 60 rpm, and with drying air at a temperature from room temperatureto as high as about 100 C., most of the time at from 40 to 70 or 90 C.,the present foams will not be completely spread over the laundry withina three minute period. In other words, some of the foam will still bepresent in the dryer after this period of time and normally at least 10%of the formula will still be in such form. The tumbling and dryingoperations will continue longer, from five minutes to an hour totaltime, and within such period all the foam will be distributed.Apparently the good distribution is also attributable in part to themoisture on the fabric that is to be conditioned and the particularcomponents of the foam, which, in combination, spread the conditioningagent over the laundry, softening it and making it less likely toaccumulate static charges when subjected to friction. Results obtainedwith the present product are even better than those resulting when longlasting foams of other compositions are used.

After treatment of the laundry according to the invention examinationindicates no spotting, greasy or oily stains or other objectionableuneven distribution of the conditioning agents. Products are soft,antistatic and are not waterproofed, even after repeated treatments.

The following examples illustrate various embodiments of the invention.Unless otherwise indicated, all parts are by weight and all temperaturesare in C.

EXAMPLE 1 Coconut oil fatty alkyls dimethyl glycine, aqueous Coconut oilfatty acids amidopropyl dimethyl 1 32% active ingredient, 3% inorganicsalt (chloride), tree oil and amine, 65% water.

Pressurized softening and antistatic compositions for the treatment oflaundry in an automatic laundry dryer are made of Formulas A and B bymixing the mentioned constituents in known manner, adding the mixturesto separate gas-tight valved dispensing containers (16 oz. capacity) andpressurizing such containers by addition through the valves of a 60:40mixture of Propellants 12 and 114. After filling is complete thecontainers are shaken, are tested for gas-tightness and internalpressure, and are ready for use.

From a container of such product there is discharged 20 grams ofmaterial, which, after loss of some propellant, results in aboutnineteen grams of foam, having a density of about 0.03 gram per cubiccentimeter. The pressure of the composition inside the container, about55 p.s.i.g., results in the foam produced being voluminous (almost aliter in volume). In other experiments, when the ratio of Propellants l2and 114 is 30:70 and the pressure is about 25 p.s.i.g., the density ofthe foam made is higher (0.05 to 0.1 g./cc.) and the volume iscorrespondingly diminished. In other cases, these foams are dischargedin separate foam balls, so that from two to four of these are employedto furnish the approximately nineteen grams of conditioning composition(less same propellant). The loss of propellant is mostly of Propellant12.

Five seconds after discharging the composition (this description is forthe plurality of mentioned formulas and foams) on top of an eight pound(dry basis) charge of mixed damp laundry (approximately 45% moisturecontent), which laundry is composed approximately half of cotton andhalf of synthetic fabrics, the dryer is started. The synthetics chargedinclude permanent or durable press treated polyester-cotton blends in65:35 proportions, Dacron, acetates, acrylics and nylons. The permanentpress materials comprise a greater proportion of the synthetics, beingabout 35% of the total charge. For test purposes, some of the permanentpress fabric is a light blue in color so that oily or greasy deposits ofexcessive amounts of materials such as fabric conditioners can be easilydiscerned thereon, especially after the products are pressed, eitherwith a hot iron or by steam pressing.

The dryer is started in motion immediately after addition of theconditioning foam, with drying gas at about 70 to C. being admitted andthe dryer revolving at about 30 r.p.m. After three minutes of operationthe dryer is halted and the drying foams are observed. It is noted thatapproximately 20% of the foam has not at that time been rubbed onto thelaundry or otherwise removed from the foam body. In other words,approproximately 20% of the foam still remains intact in the dryer,sometimes locating on a dryer rib or on the door. Drying is continuedand after five minutes total drying time, during which period thetemperature of the outlet air from the dryer is about 45 C., becauseheat is absorbed from the drying air due to the evaporation of water,the contents of the dryer are again examined and no foam is found.Subsequently, drying is continued for another 40 minutes, until all thelaundry is thoroughly dried and has had conditioning agents distributedevenly over it.

The laundry treated, after it has cooled down, is checked for softeningand antistatic properties. With respect to each article of laundry it isfound that the treated materials are noticeably less prone to holdstatic electricity charges and the items are found to be pleasantly softto the touch, especially when compared to controls not treated with theconditioning foam. No oily or greasy stains are found on any of theitems treated with either of the formulas given, even after pressingwith a hot iron.

In modifications of the experiment, the foam is applied at differenttimes during the drying cycle, with half of it being appliedimmediately, a quarter after five minutes and another quarter after anadditional ten minutes. No significant differences in product propertiesresult and, because of the inconvenience of partial applications of theconditioners, the preferred method of application is at the beginning ofdrying, as previously described.

In modifications of the formulas, the proportions of the dimethylglycine compounds of the formulas given in the specification are changedto 1, 2, 5, 10 and 20% of the active material, with the propellantmixture concentration being changed accordingly, to 52, 51, 48, 43 and33%, respectively. As would be expected, with the lesser proportions ofthe dimethyl glycine derivative compounds, 1% and less, the conditioningobtained is not as good as with 2-5%. Less than 1% active dimethylglycine DMG compound gives insufiicient conditioning. Surprisingly, from2 to 5% of the DMG compound gives softening about as good as with 6 to20% .Above 20% the product becomes too concentrated, danger of stainingincreases and it is uneconomical. In all the formula variations thepercent of water is maintained in the 30 to 60% range. To avoid makingthe foam soupy and too readily smeared onto the laundry being treatedthe mois 111 ture content is held below 75% but enough is used to forman emulsion.

When the proportion of triethanolamine stearate (commercial doublepressed stearic acid derivative) or other lower alkanolamine higherfatty acids soap in the composition is changed to 0.3%, 4% and 20%, theconditioning effects vary, being less with the lower percentage andgreater with the higher percentages of triethanolamine stearate. Thealkanolamine soap also acts to distribute the DMG compound evenly overthe laundry so the more present, within the 0.1 to 30% range, the betterthe distribution obtained. The foams made with the greater proportionsof the soap are stronger and take longer to be destroyed in the dryer.Changes in the percentage of water within the 20 to 70% range do notsignificantly adversely affect the conditioning properties of thecomposition, although stronger foams are obtained with the lowerproportions of water. Modifications of the proportion of alkanolamidewithin the range of the specification are operative in the formulasgiven, with good results being obtained when 0.1 to 0.5% is used. Thealkanolamide has a good antistatic action and acts as a leveling agent,too. Stearyl dimethyl amine oxide, present to the extent of 1 to 20% ofthe composition, e.g., 1 and adds conditioning and release actionswithout hurting physical properties of the foam. Of course, increases inthe percentages of plasticizer or humectant compounds have the effect ofincreasing the solubility or application rate of the conditioning agentsin the dryer, in addition to making them tougher and less liable tobreaking apart due to forces imposed on them. Changes in humectant orglycerol content to 0.3%, 4% and result in useful foams being produced.The alcohol used to solubilize the perfume may be diminished to 0.1% orincreased to 5%. In most cases where adjuvants are present or componentsare increased, the propellant and water contents can be decreasedaccordingly. The pH may be varied from the present 7.5 to 6 to 9 by theaddition of acids, alkalies, buffers or similar adjuvants. Sometimes theliquefied gas may be replaced with pressurized gas and as little as 1%of the latter can give the desired pressure and foam, preferably whenused together with the liquefied gas.

In addition to changing the proportions of the various components ofthese compositions and the types thereof and making pluralities of suchchanges, the weights of active conditioning agents applied may also bealtered. Thus, useful conditioning is obtained by employing enough foamto deposit /2, 3 and 6 grams of active softening agents per eight poundsof laundry. Generally, the lesser amount which gives good conditioningwill be employed.

When two to five percent of either a nonionic or anionic conditioningagent, such as nonyl phenoxy polyethoxy ethanol (Igepal CO 880) orlauryl alcohol sulfate,replaces a similar proportion of propellant, theadded conditioning effects are noted. When different propellants areemployed, such as an 85:15 ratio of isobutane and propane, orcorresponding proportions of the preferred chlorofluorinated lowerhydrocarbons, good foams are produced. However, usually the use ofstraight hydrocarbon propellant systems will be avoided, due to a desireto prevent even the possibility of any combustion of the propellantduring use. Use of soluble compressed gases, e.g., nitrogen, is feasiblebut the foams are not as good as those of the liquefied gases.

Also, in the formulas described when, in addition to the proportionsbeing varied, others of the described equivalent active and supportingmaterials are utilized, e.g., other mentioned dimethyl glycinederivatives and corresponding sulfobetaines, diethanolamine cocate,propylene glycol, and stearic diisopropanolamide, corresponding goodconditioning foams are produced and laundry and other textile materialsand fabrics being conditioned with these foams by tumbling under typicalautomatic laundry dryer conditions or their equivalents aresatisfactorily softened and made static free.

EXAMPLE 2 Glycerine Laurie myrlstic diethanolann'de Polyethyleneemulsion, aqueous Z water, deionized 60:40 mixture of Propellant 12(dichlorodiflurometlhane; and Propellant 114 (dichlorotetrafluoroet ane1 Accompanied by 1.2% salt and amine and 26% water. 2 32% polyethyleneof molecular weight of 2,0002,200, 8% polyethoxy nonyl phenol (10-20ethoxies), 60% water.

The above pressurized softening and antistatic compositions are madeaccording to standard techniques, as described in Example 1, and aretested by the method described therein. Instead of using thetriethanolamine stearate or similar alkanolamine soap, triethanolamineand stearic acid may be employed and the soap may be in situ. Similarly,instead of employing the full amount of one of the DMG compounds, amixture of equal parts thereof may be utilized.

When such materials are tested by the method described in Example 1, theproducts are found to be very satisfactorily softened and also, areantistatic. They are of softness characteristics very similar to thebest obtained with cationic softening agents, even in the samecompositions, despite the fact that the described betaines have not beenconsidered to be as good in softening as the quaternary and othercationic softening compounds. Furthermore, they do not objectionablystain laundry treated with them and do not waterproof such laundry uponrepeated applications. Laundered articles treated with the presentcompositions in an automatic laundry dryer during regular dryingoperations are noticeably superior to control laundry items.

Although the compositions of this example contain greater quantities ofDMG compound than those of Example 1, the difference in softening effectis not great. In fact, in some cases, little difference can be detectedbetween those compositions with two to five percent of DMG compound inthem and those of the present 13%.

In variations of the above formulas, myristyl dimethyl glycine andpalmityl amidoethyl dimethyl glycine are employed in place of therespective alkyl and fatty acid amido compounds. Although the softeningeffects obtained may not be as good, they are useful. Also, in suchformulas and the primary formulas of this example, when 30% of thetriethanolamine stearate is replaced by sodium or potassium stearate,the softening effects and antistatic activities are still obtained andthe leveling action of the triethanolamine stearate is not appreciablydiminished. Changes in the propellant types, to a mixture of Freons 11and 12 or isobutane and propane :15), do not charge the good quality ofthe foam, although its density may be varied somewhat in the 0.01 to 0.1./cc. range.

In the above formulations, when each is modified so as to excludenonessential components (glycerine, lauric myristic diethanolamide andpolyethylene emulsion), the products obtained are still useful softenersand the foams are sufficiently stable to last appreciable times in thedryer (three minutes or more).

The invention has been described with respect to various descriptionsand illustrative examples thereof. It is not to be so limited since itis apparent to one of skill in the art that substitutions may be madeand equivalents may be utilized without departing from the spirit of theinvention.

What is claimed is:

1. A method for conditioning damp fabrics which comprises tumble dryingsaid fabrics in a laundry dryer in the presence of a foam which normallyresists breakdown or drainage and which during tumbling does not producestaining on the fabrics, said foam being sufficiently stable so that atleast 10% of said foam remains as a foam for three minutes afterbeginning said tumble drying, said foam comprising 1 to 20% of a fabricconditioning compound of the formula:

[3? r r R CN-(CH:) ,,-N+(CHi pCo wherein R is a higher fatty alkyl ormono-unsaturated alkenyl of 9 to 19 carbon atoms when n is 1 and of tocarbon atoms when n is 0, R is hydrogen or alkyl of 1 to 3 carbon atoms,R and R are alkyls of 1 to 3 carbon atoms, In is from 1 to 5, n is 0 or1 and p is from 1 to 3, 0.1 to of a fabric conditioning loweralkanolamine higher fatty acid soap, up to 75% of a liquefied orpressurized gas propellant, and less than 75% of Water.

2. In a method for treating damp fabrics with a conditioning compositionin a revolving drum laundry dryer wherein the fabrics are tumbled whilehot air is blown through said dryer, the improvement wherein saidconditioning composition is in the form of a foam which normally resistsbreakdown or drainage and which during tumbling does not producestaining on said fabrics and which is sufiiciently stable so that atleast 10% of said foam remains as a foam for three minutes afterbeginning of the tumbling with the damp fabrics at a drum speed of from10 to 100 revolutions per minute and with dryer air at a temperature offrom 40 C. to 90 C., said foam comprising 1 to 20% of a fabricconditioning compound of the formula:

wherein R is a higher fatty alkyl of mono-unsaturated alkenyl of 9 to 19carbon atoms when n is 1 and of 10 to 20 carbon atoms when n is 0, R ishydrogen or alkyl of 1 to 3 carbon atoms, R and R are alkyls of 1 to 3carbon atoms, in is from 1 to 5, n is 0 or 1 and p is from 1 to 3, 0.1to 30% of a fabric conditioning lower alkanolamine higher fatty acidsoap, up to 75 of a liquefied or pressurized gas propellant, and lessthan 75 of water.

3. In a method as defined in claim 1 wherein in the formula of thefabric conditioning compound R is a higher fatty alkyl of 9 to 13 carbonatoms When n is 1 and 10 to 14 carbon atoms when n is 0, R is hydrogen,R and R are methyl, m is 3 and p is 1, the lower alkanolamine higherfatty acid soap is a triethanolaminc soap of higher fatty acids of 16 to20 carbon atoms and the foam contains from 1 to 15% of a fabricconditioning compound Within the given formula, 1 to 10% of triethanolamine higher fatty acid soap, 35 to of liquefied gas propellant, and 20to 60% of water.

4. In a method as defined in claim 3 wherein the fabric conditioningcompound within the given formula is a coconut oil fatty alkyl amine ofdimethyl glycine, the soap is triethanolamine stearate and the foamcomprises from 0.1 to 20% of a humectant and from 0.05 to 2% of a higherfatty acid di-lower alkanolamide.

5. In a method as defined in claim 1 wherein the fabric conditioningcompound within the given formula is a coconut oil fatty acidsamiclopropyl dimethyl glycine, the soap is triethanolamine stearate andthe foam comprises from 0.1 to 20% of a humectant and from 005 to 2% ofa higher fatty acid di-lower alkanolamide.

6. In a method as defined in claim 2 wherein the foam is produced bydispensing said conditioning composition from a pressurized dispensingcontainer.

References Cited UNITED STATES PATENTS 3,650,816 3/1972 Rudy et al117-109 1,948,568 2/1934 Faber et a1 8-138 X 2,023,013 12/1935 Faber eta1 8149.1 X 2,655,480 10/1953 Spitzer et a1. 252305 X 2,255,082 9/1941Orthnel' et a1 260501.13 3,360,550 12/1967 Cowen et al. 2528.8 X3,442,692 5/1969 Gaiser 117-1395 X 3,676,199 7/1972 Hewitt et a1.117139.5 X 3,686,025 8/1972 Morton 2528.8 X 2,313,573 3/1943 Orthner eta1. 260-501.l3 X

HERBERT B. GUYNN, Primary Examiner US. Cl. X.R.

